WO2004078768A2 - Isocyanate adducts - Google Patents
Isocyanate adducts Download PDFInfo
- Publication number
- WO2004078768A2 WO2004078768A2 PCT/GB2004/000916 GB2004000916W WO2004078768A2 WO 2004078768 A2 WO2004078768 A2 WO 2004078768A2 GB 2004000916 W GB2004000916 W GB 2004000916W WO 2004078768 A2 WO2004078768 A2 WO 2004078768A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adduct
- isocyanate
- diisocyanate
- carbon atoms
- alkyl
- Prior art date
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 12
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 230000008878 coupling Effects 0.000 claims abstract description 3
- 238000010168 coupling process Methods 0.000 claims abstract description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 9
- -1 ra-butyl isocyanate Chemical compound 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 claims description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- HHIRBXHEYVDUAM-UHFFFAOYSA-N 1-chloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1 HHIRBXHEYVDUAM-UHFFFAOYSA-N 0.000 claims description 2
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 claims description 2
- MFUVCHZWGSJKEQ-UHFFFAOYSA-N 3,4-dichlorphenylisocyanate Chemical compound ClC1=CC=C(N=C=O)C=C1Cl MFUVCHZWGSJKEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- RWHJATFJJVMKGR-UHFFFAOYSA-L dibutyltin(2+);methanethioate Chemical compound [O-]C=S.[O-]C=S.CCCC[Sn+2]CCCC RWHJATFJJVMKGR-UHFFFAOYSA-L 0.000 claims description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 claims description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 8
- 239000011496 polyurethane foam Substances 0.000 description 8
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 5
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 0 CCCC(C)(O*OP(*)(C(*)(CC)N)=O)P(*)(O)=O Chemical compound CCCC(C)(O*OP(*)(C(*)(CC)N)=O)P(*)(O)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- OOCYPIXCHKROMD-UHFFFAOYSA-M phenyl(propanoyloxy)mercury Chemical compound CCC(=O)O[Hg]C1=CC=CC=C1 OOCYPIXCHKROMD-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
Definitions
- This invention relates to alkylene-bridged alkyl phosphonates and in particular to isocyanate adduets thereof, to the use of such adduets as, or in connection with, flame-retardants and to articles made flame-relardanl
- Flame-relardants are incorporated into many products on the grounds of safely in order to control the spread of fire through the product.
- Flame- retardants can, for example, act by causing rapid extinguishing of flames, or by making the product difficult to set alight.
- flame-retardants have conventionally been used to treat fabrics, soft furnishings and the like, and have been incorporated inter alia into foams, paints and resins such as epoxy resins, many other applications are now being actively pursued, especially within the electronics, automotive, aerospace and construction industries .
- Polyurethane foams are widely used for seating components of all kinds, especially seating components for automobiles. These foams are not inherently flame-retardant (indeed, the products of combustion of many polyurethane foams are very toxic) and therefore some flame-retardant ingredient is required.
- the said European Patent Application 0 845 474 provided halogen-free oligomeric or polymeric alkylene-bridged alkyl phosphonates having the general formula (I) :
- n is a whole number from 3 to 20;
- R 1 and R 5 are each alkyl groups having from 1 to 6 carbon atoms;
- R 2 and R 4 are each alkyl groups having from 2 to 10 carbon atoms;
- R is an alkyl group having from 6 to 10 carbon atoms which acts as an "alkylene bridging" group.
- the present invention provides an adduct of an isocyanate and a halogen-free oligomeric or polymeric phosphonate or organophosphate .
- the present invention also provides the use of such an adduct as, or in connection with, a flame-retardant.
- the present invention further provides an article comprising a flame- retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as hereinbefore described.
- the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate in the presence of a catalyst.
- organophosphonate is used to form the adduct
- organophosphate is used, it is suitably of general formula (II) below:
- R 1 is H or an alkyl group having from 2 to 10 carbon atoms
- 2 is an alkyl or aryl group having from 2 to 10 carbon atoms
- R 3 is an alkyl or aryl group having from 2 to 10 carbon atoms
- R 7 is an alkyl or aryl group having from 2 to 10 carbon atoms
- R 8 is an alkyl or aryl group having from 2 to 20 carbon atoms
- n is a whole number from 1 to 20
- the isocyanate may be selected from the group consisting of tolulene 2,4 isocyanate, tolulene 2,6 diisocyanate, 4,4' methylene diisocyanate, 2,4' methylene diphenyl diisocyantate, polymeric methylene diphenyl diisocyanate, j ⁇ -phenylene diisocyanate, naphthalene-1,5- diisocyanate, 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, « -butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl iso
- the catalyst may preferably be selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionate, lead octoate, alkali-metal salts, calcium carbonate and ferric acetylacetonate.
- a 5L glass oil -jacketed reactor was fitted with a reflux condenser, temperature probe, and an overhead mechanical stirrer. Under nitrogen, oligomeric butyl phosphonate (4200g) (as in Example 1 of EP 0 845 474) and slannous octoate (1.26g) were charged into the reactor at room temperature and heated to 100°C. MDI (a mixture of 2,4'- and 4,4'- diphenylmethane diisocyanate, 336g) was added to the reactor via a dropping funnel over 30 minutes. During the addition, the temperature in the reactor rose by 5-10°C. The reaction mixture was then heated to 110°C, and aged for twelve hours. The product obtained was a pale yellow viscous liquid (4488g, 99% yield).
- Example 1 The product of the Example 1 (above) and the oligomeric butyl phosphonate as in Example 1 of EP 0 845 474, were each used as the flame retardant additive for the production of a high resilience polyurethane foam.
- the quantities used and the results obtained are shown in Table 1 (below) .
- Cream Time S 19 Foam Collapse Rise Time S 121 n/a Density Kg/m 3 25.10 n/a
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
An adduct of an isocyanate and a halogen-free oligomeric or polymeric alkyl phosphonate or organophosphate. The adduct may be made by coupling the isocyanate and the phosphonate or phosphate in the presence of a catalyst. Also disclosed is the use of the adduct as, or in connection with, a flame-retardant. The adduct can be used to render foam flame-retardant.
Description
ISOCYANATE ADDUCTS
This invention relates to alkylene-bridged alkyl phosphonates and in particular to isocyanate adduets thereof, to the use of such adduets as, or in connection with, flame-retardants and to articles made flame-relardanl
Flame-relardants are incorporated into many products on the grounds of safely in order to control the spread of fire through the product. Flame- retardants can, for example, act by causing rapid extinguishing of flames, or by making the product difficult to set alight. Whilst flame-retardants have conventionally been used to treat fabrics, soft furnishings and the like, and have been incorporated inter alia into foams, paints and resins such as epoxy resins, many other applications are now being actively pursued, especially within the electronics, automotive, aerospace and construction industries .
Polyurethane foams are widely used for seating components of all kinds, especially seating components for automobiles. These foams are not inherently flame-retardant (indeed, the products of combustion of many polyurethane foams are very toxic) and therefore some flame-retardant ingredient is required.
Many of the flame retardants conventionally used in connection with polyurethane foam seating components are found to have a tendency to migrate and/or volatilise from the foams with age. This tendency is particularly disadvantageous in the case of polyurethane foam components of automobile seating, where the migration and/or volatilisation of the flame relardanl leads to "fogging" of glass surfaces, such as windows and instrument panels. Accordingly, in our published European Patent Application 0 845 474, we disclose that certain halogen-free oligomeric
or polymeric alkylene-bridged alkyl phosphonates confer acceptable flame-retardant properties on, inter alia, polyurethane foams.
The said European Patent Application 0 845 474 provided halogen-free oligomeric or polymeric alkylene-bridged alkyl phosphonates having the general formula (I) :
where n is a whole number from 3 to 20;
R1 and R5 (which may be the same or different) are each alkyl groups having from 1 to 6 carbon atoms;
R2 and R4 (which may be the same, or different) are each alkyl groups having from 2 to 10 carbon atoms;
and R is an alkyl group having from 6 to 10 carbon atoms which acts as an "alkylene bridging" group.
We have found that the addition to a polyurethane foam-forming reaction mixture of phosphonates according to formula (I) or phosphates according to formula (II) , below, can have a detrimental effect on the mechanical properties of polyurethane foam in some foam formulations (particularly in the case of high resilience foams) , or cause the foam to collapse during manufacturing.
We have now found that this detrimental effect can be avoided by forming an isocyanate adduct of a phosphonate according to formula (I) or of a phosphate according to formula (II), below, prior to commencing the foam-forming reaction.
We have also found that it is possible to enhance the low-fogging properties of these alkylene-bridged alkyl phosphonates, when used as flame-retardants for polyurethane foams.
Accordingly, the present invention provides an adduct of an isocyanate and a halogen-free oligomeric or polymeric phosphonate or organophosphate .
The present invention also provides the use of such an adduct as, or in connection with, a flame-retardant.
The present invention further provides an article comprising a flame- retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as hereinbefore described.
Suitably, the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate in the presence of a catalyst.
Where an organophosphonate is used to form the adduct, it is suitably of general formula (I) above. Where an organophosphate is used, it is suitably of general formula (II) below:
2 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R3 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R7 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R8 is an alkyl or aryl group having from 2 to 20 carbon atoms;
and n is a whole number from 1 to 20
Suitably, the isocyanate may be selected from the group consisting of tolulene 2,4 isocyanate, tolulene 2,6 diisocyanate, 4,4' methylene diisocyanate, 2,4' methylene diphenyl diisocyantate, polymeric methylene diphenyl diisocyanate, jø-phenylene diisocyanate, naphthalene-1,5- diisocyanate, 1,6 hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, « -butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, and -toluenesulfonyl isocyanate.
The catalyst may preferably be selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionate, lead octoate, alkali-metal salts, calcium carbonate and ferric acetylacetonate.
The invention will now be illustrated with reference to the following example.
Example 1
A 5L glass oil -jacketed reactor was fitted with a reflux condenser, temperature probe, and an overhead mechanical stirrer. Under nitrogen, oligomeric butyl phosphonate (4200g) (as in Example 1 of EP 0 845 474) and slannous octoate (1.26g) were charged into the reactor at room temperature and heated to 100°C. MDI (a mixture of 2,4'- and 4,4'- diphenylmethane diisocyanate, 336g) was added to the reactor via a dropping funnel over 30 minutes. During the addition, the temperature in the reactor rose by 5-10°C. The reaction mixture was then heated to 110°C, and aged for twelve hours. The product obtained was a pale yellow viscous liquid (4488g, 99% yield).
Example 2
The product of the Example 1 (above) and the oligomeric butyl phosphonate as in Example 1 of EP 0 845 474, were each used as the flame retardant additive for the production of a high resilience polyurethane foam. The quantities used and the results obtained are shown in Table 1 (below) .
Table 1
High Resilience Foam Phosphonate of Control Formulations Invention Phosphonate
Standard High Resilience 100.00 100.00 Polymeric Polyol (OH value = 30-34) Water Parts .45 45
(a) Catalyst I Parts .10 10
(b) Catalyst II Parts .06 06 Diethanolamine Parts .10 10
(c) Surfactant Parts .40 0 40 Stannous Octoate Parts .21 0 21 Toluene Di-isocyanate Index 108 108
(d) Phosphonate of Invention Parts ^.00
(e) Control Phosphonate Parts 9.00
Cream Time S 19 Foam Collapse Rise Time S 121 n/a Density Kg/m3 25.10 n/a
Indicative Federal Motor Vehicle Safety Standard 302 Performance
Burn Length Mm n/a
Burn Time n/a
Rating Self -Extinguishing n/a
Notes to Table 1:
(a) An amine catalyst comprising 33% diaza-bicyclo-octane and 67% dipropylene glycol, available as DABCO*33LV
(b) An amine catalyst comprising 70% bis(2-dimethylaminoethyl) ether and 30% dipropylene glycol, available as NIAX*A1
(c) A polyether-modified polysiloxane, available as TEGOSTAB*B8681
(d) The product of Example 1 i.e. oligomeric butyl phosphonate/isocyanate adduct.
(e) the oligomeric butyl phosphonate as in EP 0 845 474, Example 1. *DABCO, NIAX and TEGOSTAB are Registered Trade Marks.
Claims
1. An adduct of an isocyanate and ; a halogen-free oligomeric or polymeric alkyl phosphonate or organophos'
2. An adduct as claimed in claim 1 in which the isocyanate/phosphonate/phosphate adduct is made by coupling the isocyanate and the phosphonate or phosphate in the presence of a catalyst.
3. An adduct as claimed in any one of the preceding claims in which an organophosphonate is used to form the adduct and is of the general formula (I):
R1 and R5 (which may be the same, or different) are each alkyl groups having form 1 to 6 carbon atoms;
R2 and R4 (which may be the same or different) are each alkyl groups having from 2 to 10 carbon atoms; and
R3 is an alkyl group having from 6 to 10 carbon atoms, which acts as an "alkylene bridging" group.
4. An adduct as claimed in either of claims 1 or 2, in which an organophosphate is used to form the adduct and is of the general formula (II):
wherein n is a whole number from 1 to 20;
R1 is H or an alkyl or aryl group having from 2 to 10 carbon atoms;
R2 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R3 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R7 is an alkyl or aryl group having from 2 to 10 carbon atoms;
R8 is an alkyl or aryl group having from 2 to 20 carbon atoms.
5. An adduct as claimed in any one of the preceding claims in which the isocyanate is selected from the group consisting of; tolulene 2,4-diisocyanate, tolulene 2,6-diisocyanate, 4,4' -methylene diisocyanate, 2, 4 '-methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, ?-phenylene diisocyanate, naphthalene- 1,5 -diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, methyl isocyanate, ra-butyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, and j9-toluenesulfonyl isocyanate.
6. An adduct as claimed in any one of the preceding claims in which the catalyst is selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, phenylmercuric propionale, lead octoate, alkali-metal salts, calcium carbonate and ferric acelylacelonate.
7. The use of an adduct as claimed in any one of claims 1 to 6 as, or in connection with, a flame-retardant.
8. An article comprising a flame-retardant foam, wherein the foam is rendered flame-retardant by means of an adduct as claimed in any one of claims 1 to 6.
9. An adduct substantially as described herein with reference to the examples.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0304831.1 | 2003-03-04 | ||
| GB0304831A GB0304831D0 (en) | 2003-03-04 | 2003-03-04 | Isocyanate adducts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004078768A2 true WO2004078768A2 (en) | 2004-09-16 |
| WO2004078768A3 WO2004078768A3 (en) | 2004-12-02 |
Family
ID=9954018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2004/000916 WO2004078768A2 (en) | 2003-03-04 | 2004-03-04 | Isocyanate adducts |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB0304831D0 (en) |
| WO (1) | WO2004078768A2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0845474A1 (en) * | 1996-11-13 | 1998-06-03 | ALBRIGHT & WILSON UK LIMITED | Alkylene-bridged alkyl phosphonates |
| US5880243A (en) * | 1997-04-23 | 1999-03-09 | Weyerhaeuser Company | Fire retardant composite products of cellulose impregnated with isocyanate compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762225A (en) * | 1993-08-25 | 1995-03-07 | Akzo Kashima Ltd | Flame retardant composition for flexible polyurethane foam |
-
2003
- 2003-03-04 GB GB0304831A patent/GB0304831D0/en not_active Ceased
-
2004
- 2004-03-04 WO PCT/GB2004/000916 patent/WO2004078768A2/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0845474A1 (en) * | 1996-11-13 | 1998-06-03 | ALBRIGHT & WILSON UK LIMITED | Alkylene-bridged alkyl phosphonates |
| US5880243A (en) * | 1997-04-23 | 1999-03-09 | Weyerhaeuser Company | Fire retardant composite products of cellulose impregnated with isocyanate compositions |
Non-Patent Citations (2)
| Title |
|---|
| DATABASE CAPLUS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BORISOV, G. ET AL: "Preparation of phosphorus-containing and phosphorus- and chlorine-containing polyurethanes from bisÄmethoxyhydroxy(alkyl, phenyl)methanephosphonoÜoxyalkanes" XP002291525 retrieved from STN Database accession no. 1975:459996 & IZVESTIYA NA OTDELENIETO ZA KHIMICHESKI NAUKI (BULGARSKA AKADEMIYA NA NAUKITE) , 6(3), 577-84 CODEN: IOKNA5; ISSN: 0525-0889, 1973, * |
| DATABASE CAPLUS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TAKIMOTO, HIDEO ET AL: "Fireproofing agents for soft polyurethane foams" XP002291526 retrieved from STN Database accession no. 1995:636260 & JP 07 062225 A2 (KASHIMA KOGYO KK, JAPAN) 7 March 1995 (1995-03-07) * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004078768A3 (en) | 2004-12-02 |
| GB0304831D0 (en) | 2003-04-09 |
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